TY - JOUR
T1 - Plutonium Hybrid Materials
T2 - A Platform to Explore Assembly and Metal-Ligand Bonding
AU - Surbella, Robert G.
AU - Ducati, Lucas C.
AU - Schofield, Mark H.
AU - McNamara, Bruce K.
AU - Pellegrini, Kristi L.
AU - Corbey, Jordan F.
AU - Schwantes, Jon M.
AU - Autschbach, Jochen
AU - Cahill, Christopher L.
N1 - Funding Information:
The primary source of support for this research is the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, Heavy Element Chemistry program under grant DE-FG02-05ER15736 at GWU. Crystal structure refinement, computational data interpretation, and manuscript preparation were supported by a grant to PNNL from the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, Heavy Element Chemistry program. R.G.S. also acknowledges support from the National Technical Nuclear Forensic Center, which supported the crystal growth and crystallography experiments. M.S. gratefully acknowledges the computing resources provided by the High-Performance Computing Cluster operated by Research Technology Services at George Washington University for the work conducted using the B3LYP functional. The noncovalent interaction and plutonium bonding analyses conducted using the M06-2X functional were carried out by L.C.D. and J.A. with support from the DOE Heavy Elements Program grant DE-SC0001136. L.C.D. is grateful for a fellowship from the São Paulo Research Foundation (FAPESP) 2017/17750-3, 2020/10246-0 and for the fellowship CNPq #306844/2020-6. We acknowledge the National Laboratory for Scientific Computing (LNCC/MCTI, Brazil, SDumont supercomputer) and the Center for Computational Research (CCR) at the University at Buffalo for providing high-performance computing resources. We are thankful to Dr. Ginger Sigmon of the University of Notre Dame for collecting the single crystal X-ray diffraction data at 110(2) K.
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/11/14
Y1 - 2022/11/14
N2 - We report the synthesis of five new hybrid materials containing the [PuCl6]2-anion and charge-balancing, noncovalent interaction donating 4-X-pyridinium (X = H, Cl, Br, I) cations. Single crystals of the title compounds were grown and harvested from acidic, chloride-rich, aqueous media, and their structures were determined via X-ray diffraction. Compounds 1-4, (4XPyH)2[PuCl6], and 5, (4IPyH)4[PuCl6]·2Cl, exhibit two distinct sheet-like structure types. Structurally relevant noncovalent interactions were tabulated from crystallographic data and verified computationally using electrostatic surface potential maps and the quantum theory of atoms in molecules (QTAIM). The strength of the hydrogen and halogen bonds was quantified using Kohn-Sham density functional theory, and a hierarchy of acceptor-donor pairings was established. The PuIV-Cl bonds were studied using QTAIM and natural localized molecular orbital (NLMO) analyses to delineate the underlying bond mechanism and hybrid atomic orbital contributions therein. The results of the PuIV-Cl bond analyses were compared across compositions via analogous treatments of previously reported [PuO2Cl4]2-and [PuCl3(H2O)5] molecular units. The Pu-Cl bonds are predominately ionic yet exhibit small varying degrees of covalent character that increases from [PuCl3(H2O)5] and [PuO2Cl4]2-to [PuCl6]2-, while the participation of the Pu-based s/d and f orbitals concurrently decreases and increases, respectively.
AB - We report the synthesis of five new hybrid materials containing the [PuCl6]2-anion and charge-balancing, noncovalent interaction donating 4-X-pyridinium (X = H, Cl, Br, I) cations. Single crystals of the title compounds were grown and harvested from acidic, chloride-rich, aqueous media, and their structures were determined via X-ray diffraction. Compounds 1-4, (4XPyH)2[PuCl6], and 5, (4IPyH)4[PuCl6]·2Cl, exhibit two distinct sheet-like structure types. Structurally relevant noncovalent interactions were tabulated from crystallographic data and verified computationally using electrostatic surface potential maps and the quantum theory of atoms in molecules (QTAIM). The strength of the hydrogen and halogen bonds was quantified using Kohn-Sham density functional theory, and a hierarchy of acceptor-donor pairings was established. The PuIV-Cl bonds were studied using QTAIM and natural localized molecular orbital (NLMO) analyses to delineate the underlying bond mechanism and hybrid atomic orbital contributions therein. The results of the PuIV-Cl bond analyses were compared across compositions via analogous treatments of previously reported [PuO2Cl4]2-and [PuCl3(H2O)5] molecular units. The Pu-Cl bonds are predominately ionic yet exhibit small varying degrees of covalent character that increases from [PuCl3(H2O)5] and [PuO2Cl4]2-to [PuCl6]2-, while the participation of the Pu-based s/d and f orbitals concurrently decreases and increases, respectively.
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U2 - 10.1021/acs.inorgchem.2c02084
DO - 10.1021/acs.inorgchem.2c02084
M3 - Article
C2 - 36305869
AN - SCOPUS:85141577747
SN - 0020-1669
VL - 61
SP - 17963
EP - 17971
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 45
ER -